CN118085850A - Temperature ratio fluorescent probe based on triplet state-triplet state annihilation up-conversion luminescence and preparation method and application thereof - Google Patents
Temperature ratio fluorescent probe based on triplet state-triplet state annihilation up-conversion luminescence and preparation method and application thereof Download PDFInfo
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- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
- G01K11/20—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using thermoluminescent materials
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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Abstract
The invention discloses a temperature ratio fluorescent probe based on triplet-triplet annihilation up-conversion luminescence, and a preparation method and application thereof. The temperature ratio fluorescent probe comprises thermally-activated up-conversion crystallites and non-thermally-activated up-conversion crystallites; the thermally-activated up-conversion crystallites comprise a first photosensitizer and a first triplet annihilator, and the non-thermally-activated up-conversion crystallites comprise a second photosensitizer and a second triplet annihilator; wherein the excitation wavelength of the first photosensitizer is the same as that of the second photosensitizer, and the first photosensitizer and the second photosensitizer are selected from metal complexes absorbed in a near infrared region of 600-1000 nm. By utilizing the characteristics of different luminescent colors and opposite response of luminescent intensity to temperature change of the two upconversion microcrystals, the obtained temperature ratio fluorescent probe has the characteristics of higher relative sensitivity, wide temperature test range, visual temperature change and the like, can realize non-contact temperature detection under near infrared light irradiation, and has wide application prospect in the field of temperature sensing.
Description
Technical Field
The invention relates to the technical field of organic luminescent materials. More particularly, to a temperature ratio fluorescent probe based on triplet-triplet annihilation up-conversion luminescence, and a preparation method and application thereof.
Background
With the development of science and technology, the requirements for measuring accuracy of a plurality of physical quantities are becoming higher and higher nowadays. The temperature is one of frequently used physical quantities, and has higher requirements for accurate measurement of the temperature in electronic devices, aerospace, environmental monitoring, scientific research and industrial production. However, many conventional contact thermometers, such as thermal expansion thermometers, pressure thermometers, thermocouple thermometers, resistance thermometers, do not meet the needs of these applications. The fluorescence temperature probe can realize indirect measurement of temperature based on the change of fluorescence intensity caused by the change of molecular transition rate along with temperature, but in practical application, a single excited state fluorescence temperature sensing system can be affected by uneven distribution of probe molecules, change of molecular concentration and the like, and errors in measurement are easily caused. The ratio type fluorescent probe system has self-calibration property, and can avoid errors caused by factors such as uneven molecular distribution. The ratio-type fluorescent probe is gradually an object of wide attention of researchers due to the advantages of higher resolution, higher sensitivity, shorter response time and the like.
The temperature ratio fluorescent probe is mostly constructed based on the differential response of two fluorescence intensities with different wavelengths to temperature, two luminescence can come from different luminescent species or different excitation states of the same compound, and the response modes of the two fluorescence intensities to temperature are different: for example, fluorescence at one wavelength varies significantly with temperature, while fluorescence at another wavelength is unresponsive or weakly responsive to temperature; or the response change trend of the fluorescence intensity of two wavelengths to the temperature is opposite, which is more beneficial to the improvement of the sensitivity.
The near infrared light energy is low, the penetrability is strong, the damage to the material is small, but the material cannot be visualized, the up-conversion luminescent material can convert the near infrared light with low energy into visible light with high energy, the remote and deep visual detection is realized, meanwhile, the near infrared light has relatively weak background light, the influence of stray light generated by a pumping light source on signal light can be effectively reduced, the measurement precision is improved, although the temperature probe based on the traditional inorganic rare earth up-conversion nano particles is developed, the temperature probe depends on single-emission fluorescence, the influence of the environment is large, and the double-emission fluorescence depends on the accurate tuning of the concentration of two luminescent units, so that the practical application is not facilitated. The triplet-triplet annihilation up-conversion (TTA-UC) material has the characteristics of low excitation power, high up-conversion efficiency, different up-conversion systems have different sensitivity to temperature, and the like, and has the condition for preparing a temperature ratio fluorescent probe, but the temperature ratio fluorescent probe has low sensitivity due to few types of selectable near infrared absorption photosensitizers, and the detection temperature range is limited, so that the temperature visualization cannot be realized. For example, 2021, song Yanlin has tried to coat TTA-UC system in micelle, and the ratio fluorescent probe is formed by up-conversion luminescence and down-conversion luminescence of single up-conversion system, but the temperature detection range is narrow, only 30-60 ℃, and visualization cannot be achieved when excitation light is 532nm, which severely limits practical application. Therefore, there is a need to develop more TTA-UC up-conversion materials using near infrared absorbing metal complexes as photosensitizers to expand the temperature ratio fluorescence type, facilitate non-contact temperature measurement deeper in the object, and realize the temperature visualization effect.
Disclosure of Invention
In order to solve the above problems, a first object of the present invention is to provide a temperature ratio fluorescent probe that emits light based on triplet-triplet annihilation up-conversion. The temperature ratio fluorescent probe comprises two different up-conversion materials, namely a heat-activated up-conversion microcrystal and a non-heat-activated up-conversion microcrystal, and can be applied to the field of temperature sensing with high sensitivity and visualization by utilizing the characteristics of different luminescent colors and opposite response of luminescent intensity to temperature change of the two up-conversion microcrystals.
A second object of the present invention is to provide a method for preparing the temperature ratio fluorescent probe as described above.
A third object of the present invention is to provide an application of the fluorescent probe in the field of temperature sensing using the temperature ratio as described above.
In order to achieve the first object, the present invention adopts the following technical scheme:
the invention discloses a temperature ratio fluorescent probe based on triplet-triplet annihilation up-conversion luminescence, which comprises thermally-activated up-conversion microcrystals and non-thermally-activated up-conversion microcrystals; the thermally-activated up-conversion crystallites comprise a first photosensitizer and a first triplet annihilator, and the non-thermally-activated up-conversion crystallites comprise a second photosensitizer and a second triplet annihilator;
Wherein the excitation wavelength of the first photosensitizer is the same as that of the second photosensitizer, and the first photosensitizer and the second photosensitizer are selected from metal complexes absorbed in a near infrared region of 600-1000 nm.
In the invention, a core component of the temperature ratio fluorescent probe is composed of heat-activated up-conversion microcrystal and non-heat-activated up-conversion microcrystal, wherein the luminous intensity of the heat-activated up-conversion microcrystal gradually increases along with the increase of temperature, the luminous intensity of the non-heat-activated up-conversion microcrystal gradually decreases along with the increase of temperature, and the combination of the two up-conversion microcrystals meets the basic requirement of the temperature ratio fluorescent probe. The light emitting intensity of different up-conversion materials can be adjusted by changing the mixing proportion of the heat activated up-conversion microcrystals and the non-heat activated up-conversion microcrystals, and the position of the maximum light emitting peak wavelength of different up-conversion materials can be adjusted by changing the types of the photosensitizer and the annihilator in each up-conversion material. When the metal complex with near infrared absorption is used as a photosensitizer to prepare two upconversion microcrystals, the obtained temperature ratio fluorescent probe can realize non-contact temperature detection under near infrared light irradiation, and the influence of stray light generated by a pumping light source on signal light can be effectively reduced, so that the measurement accuracy is improved.
The temperature ratio fluorescent probe provided by the invention has a wider temperature test range and low-temperature test capability, can realize visual test of temperature change within the range of 223K-300K (namely-50 ℃ -27 ℃), and has the highest relative sensitivity of 4.5%/K.
Further, the first photosensitizer and the second photosensitizer may be the same or different, based on the premise of the same excitation wavelength, may be any one of a tetraphenyl tetrabenzoporphyrin metal complex of palladium or platinum, a rare earth complex of ytterbium as a photosensitive core, a rare earth complex of neodymium as a photosensitive core, and a rare earth complex of thulium as a photosensitive core, the foregoing is the same as the first photosensitizer, and the second photosensitizer may be the same as the first photosensitizer, and the foregoing is the same as the second photosensitizer, for example, any one of a rare earth complex in which the photosensitive core is ytterbium, a rare earth complex in which the photosensitive core is neodymium, and a rare earth complex in which the photosensitive core is thulium should ensure that the photosensitive cores are identical, the structures of the photosensitizers may be different (for example, a complex of mononuclear ytterbium, a complex of polynuclear ytterbium, etc.), and it may be understood that the first photosensitizer and the second photosensitizer are both conventional photosensitizers selected from tetraphenyl tetrabenzoporphyrin metal complexes of palladium or platinum, that is, the structures are substantially identical, and the differences are mainly due to the difference of metal types in the center of the parent nucleus (for example, tetraphenyl tetrabenzoporphyrin metal complexes of palladium or tetraphenyl tetrabenzoporphyrin metal complexes of platinum).
Further, the first photosensitizer and the second photosensitizer are selected from a diketone complex whose photosensitive core is ytterbium or palladium (II) tetraphenyl tetrabenzoporphyrin.
The first triplet annihilator and the second triplet annihilator represent different triplet annihilator types, and the first triplet annihilator may be selected from one or more of 9, 10-diphenylanthracene or a derivative thereof, 9,10- (diphenylethynyl) anthracene or a derivative thereof, 9, 10-bis [ (triisopropylsilyl) ethynyl ] anthracene, and the second triplet annihilator may be selected from one or more of rubrene, perylene tetracarboxylic diimide or a derivative thereof, according to a characteristic that the luminescence intensities of the two up-converted crystallites have opposite responses to a temperature change.
In a specific embodiment, the first photosensitizer and the second photosensitizer are selected from any one of Yb (DBM) 3(H2O)、Yb5(DBM)10(OH)5 and palladium (II) tetraphenyl tetraporphyrin, and the structures thereof are as follows:
Yb(DBM)3(H2O)、
Yb5(DBM)10(OH)5、
palladium (II) tetraphenyltetraphenylbenzoporphyrin (commercially available).
In a specific embodiment, the first triplet annihilator is selected from one of the structures shown below:
9, 10-bis [ (triisopropylsilyl) ethynyl ] anthracene,
9,10- (Diphenylethynyl) anthracene,
Derivatives of 9,10- (diphenylethynyl) anthracene,
9, 10-Diphenylanthracene,
One of the derivative structures of 9, 10-diphenyl anthracene,
Two derivative structures of 9, 10-diphenyl anthracene,
Derivative structure of 9, 10-diphenyl anthracene,
A fourth derivative structure of 9, 10-diphenylanthracene;
wherein R is any one of Cl, br and I.
In a specific embodiment, the second triplet annihilator is selected from one of the structures shown below:
3,4,9, 10-perylene tetracarboxylic diimide,
N, N' -di (ethylpropyl) perylene-3, 4,9, 10-tetracarboxylic acid (PDI),
N, N-di-N-octyl-3, 4,9, 10-perylene tetracarboxylic diimide (ODI),
Rubrene.
Further, the molar ratio of the first photosensitizer to the first triplet annihilator is 1:1 to 1:500; illustratively, the first photosensitizer and the first triplet annihilator can be present in a molar ratio of 1:1、1:5、1:10、1:15、1:20、1:25、1:30、1:35、1:40、1:45、1:50、1:60、1:70、1:80、1:90、1:100、1:200、1:300、1:400、1:500 or the like. The molar ratio of the second photosensitizer to the second triplet annihilation agent is 1:1-1:300; illustratively, the molar ratio of the second photosensitizer to the second triplet annihilator can be 1:1、1:5、1:10、1:15、1:20、1:25、1:30、1:35、1:40、1:45、1:50、1:60、1:70、1:80、1:90、1:100、1:110、1:120、1:130、1:140、1:150、1:160、1:170、1:180、1:190、1:200、1:300 or the like.
Further, in the heat-activated up-conversion crystallites, the first photosensitizer is selected from Yb (DBM) 3(H2 O), the first triplet annihilator is selected from 9,10- (diphenylethynyl) anthracene, and in the corresponding non-heat-activated up-conversion crystallites, the second photosensitizer is selected from Yb (DBM) 3(H2 O), and the second triplet annihilator is selected from N, N' -di (ethylpropyl) perylene-3, 4,9, 10-tetracarboxylic acid. In a specific embodiment, the molar ratio of the first photosensitizer to the first triplet annihilator is from 1:10 to 1:50 and the molar ratio of the second photosensitizer to the second triplet annihilator is from 1:5 to 1:20.
Further, in the thermally activated up-conversion crystallites, the first photosensitizer is selected from Yb (DBM) 3(H2 O), the first triplet annihilator is selected from 9, 10-bis [ (triisopropylsilyl) ethynyl ] anthracene, and in its corresponding non-thermally activated up-conversion crystallites, the second photosensitizer is selected from Yb (DBM) 3(H2 O, and the second triplet annihilator is selected from N, N' -di (ethylpropyl) perylene-3, 4,9, 10-tetracarboxylic acid. In a specific embodiment, the molar ratio of the first photosensitizer to the first triplet annihilator is in the range of 1:1 to 1:10 and the molar ratio of the second photosensitizer to the second triplet annihilator is in the range of 1:5 to 1:20.
Further, in the heat-activated up-conversion crystallites, the first photosensitizer is selected from Yb (DBM) 3(H2 O), the first triplet annihilator is selected from 9,10- (diphenylethynyl) anthracene, and in the corresponding non-heat-activated up-conversion crystallites, the second photosensitizer is selected from Yb (DBM) 3(H2 O), and the second triplet annihilator is selected from N, N-di-N-octylyl-3, 4,9, 10-perylenetetracarboxylic diimide. In a specific embodiment, the molar ratio of the first photosensitizer to the first triplet annihilator is from 1:10 to 1:50 and the molar ratio of the second photosensitizer to the second triplet annihilator is from 1:5 to 1:15.
Further, in the thermally activated up-conversion crystallites, the first photosensitizer is selected from Yb (DBM) 3(H2 O), the first triplet annihilator is selected from 9, 10-bis [ (triisopropylsilyl) ethynyl ] anthracene, and in the corresponding non-thermally activated up-conversion crystallites, the second photosensitizer is selected from Yb (DBM) 3(H2 O, and the second triplet annihilator is selected from N, N-di-N-octyl-3, 4,9, 10-perylene tetracarboxylic diimide. In a specific embodiment, the molar ratio of the first photosensitizer to the first triplet annihilator is in the range of 1:1 to 1:10 and the molar ratio of the second photosensitizer to the second triplet annihilator is in the range of 1:5 to 1:15.
Further, in the heat-activated up-conversion crystallites, the first photosensitizer is selected from Yb (DBM) 3(H2 O), the first triplet annihilator is selected from 9, 10-bis [ (triisopropylsilyl) ethynyl ] anthracene, and in the corresponding non-heat-activated up-conversion crystallites, the second photosensitizer is selected from Yb (DBM) 3(H2 O, and the second triplet annihilator is selected from rubrene. In a specific embodiment, the molar ratio of the first photosensitizer to the first triplet annihilator is in the range of 1:1 to 1:10 and the molar ratio of the second photosensitizer to the second triplet annihilator is in the range of 1:10 to 1:80.
Further, in the heat-activated up-conversion crystallites, the first photosensitizer is selected from Yb 5(DBM)10(OH)5, the first triplet annihilator is selected from 9,10- (diphenylethynyl) anthracene, and in the corresponding non-heat-activated up-conversion crystallites, the second photosensitizer is selected from Yb 5(DBM)10(OH)5, and the second triplet annihilator is selected from N, N' -di (ethylpropyl) perylene-3, 4,9, 10-tetracarboxylic acid. In a specific embodiment, the molar ratio of the first photosensitizer to the first triplet annihilator is from 1:1 to 1:10 and the molar ratio of the second photosensitizer to the second triplet annihilator is from 1:1 to 1:4.
Further, in the heat-activated up-conversion microcrystal, the first photosensitizer is selected from palladium (II) tetraphenyl tetrabenzoporphyrin, the first triplet annihilator is selected from 9, 10-diphenyl anthracene, the second photosensitizer is selected from palladium (II) tetraphenyl tetrabenzoporphyrin, and the second triplet annihilator is selected from rubrene. In a specific embodiment, the molar ratio of the first photosensitizer to the first triplet annihilator is in the range of 1:100 to 1:500 and the molar ratio of the second photosensitizer to the second triplet annihilator is in the range of 1:100 to 1:300.
Further, the mass ratio of the heat-activated up-conversion microcrystals to the non-heat-activated up-conversion microcrystals is 1:1-1:1000; preferably, the mass ratio of the heat-activated up-conversion microcrystals to the non-heat-activated up-conversion microcrystals is 1:1-1:50; illustratively, the mass ratio of the thermally-activated up-conversion crystallites and the non-thermally-activated up-conversion crystallites may be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, etc.
In order to achieve the second object, the present invention adopts the following technical scheme:
the invention discloses a preparation method for preparing a temperature ratio fluorescent probe, which comprises the following steps:
dispersing a first photosensitizer and a first triplet annihilation agent in an organic solvent, then adding the organic solvent into water, re-precipitating solids, stirring until the solids are uniformly mixed, standing, centrifuging, and drying to obtain heat-activated up-conversion microcrystals;
Dispersing a second photosensitizer and a second triplet annihilation agent in an organic solvent, then adding the organic solvent into water, re-precipitating solids, stirring until the solids are uniformly mixed, standing, centrifuging, and drying to obtain non-heat-activated up-conversion microcrystals;
and fully mixing the heat-activated up-conversion microcrystals and the non-heat-activated up-conversion microcrystals in proportion to obtain the temperature ratio fluorescent probe.
Further, the organic solvent is selected from one or more of tetrahydrofuran, chloroform, dimethyl sulfoxide and N, N-dimethylformamide.
Further, the stirring speed is 1000-2000r/min, and the stirring time is 0-5min and does not include 0min.
Further, the rotational speed of the centrifugation is 5000-10000r/min, and the centrifugation time is 5-10min.
Further, the standing time is 2-8h.
Further, the heat-activated up-conversion microcrystal and the non-heat-activated up-conversion microcrystal are fully mixed by directly mixing the two up-conversion microcrystals through mechanical oscillation, wherein the mixing time of the mechanical oscillation is not less than 5min.
In order to achieve the third object, the present invention adopts the following technical scheme:
the invention discloses application of a temperature ratio fluorescent probe in the field of temperature sensing.
Further, when the first photosensitizer and the second photosensitizer in the heat-activated up-conversion microcrystal and the non-heat-activated up-conversion microcrystal are selected from tetraphenyl tetrabenzoporphyrin metal complex of palladium or platinum, rare earth complex of ytterbium as a photosensitive core, rare earth complex of neodymium as a photosensitive core and rare earth complex of thulium as a photosensitive core, the temperature ratio fluorescent probe can be further applied to visual non-contact temperature monitoring of the inside of a material or a device due to the fact that the temperature ratio fluorescent probe can absorb excitation light in a near infrared region of 600-1000nm and the characteristics of high penetrability and small damage of near infrared light are utilized.
The beneficial effects of the invention are as follows:
1. the temperature ratio fluorescent probe based on triplet-triplet annihilation up-conversion luminescence provided by the invention uses the metal complex absorbed in the near infrared region of 600-1000nm as a photosensitizer, widens the variety of the temperature ratio fluorescent probe, can realize temperature detection at low temperature, has a detection range of 223K-300K and has higher relative sensitivity.
2. The triplet-triplet annihilation up-conversion luminescence-based temperature ratio fluorescent probe provided by the invention realizes non-contact temperature detection under near infrared light irradiation by utilizing the near infrared light sensitive metal complex photosensitizer, and the material fully utilizes the high penetrability of near infrared light, has little damage to the material and no background light, and can effectively reduce the influence of stray light generated by a pumping light source on signal light, thereby improving the measurement accuracy.
3. The temperature ratio fluorescent probe based on triplet state-triplet state annihilation up-conversion luminescence provided by the invention adopts two up-conversion luminescent materials with different temperature sensitivity for combination and doping, so that the ratio fluorescent change of the up-conversion luminescence to the temperature can be realized.
4. Compared with the traditional temperature ratio fluorescence sensor of pure inorganic rare earth nano particles, the temperature ratio fluorescence probe based on triplet state-triplet state annihilation up-conversion luminescence provided by the invention has the advantages that two groups of solid-state microcrystals are prepared by different thermal activation and non-thermal activation systems according to different temperature responsiveness, disorder of energy transfer of the photosensitizer and annihilation agent between the two groups of microcrystals is avoided, different doping ratios of the two up-conversion microcrystals can be realized, good linear correlation relationship is presented, and the temperature ratio fluorescence probe based on triplet state annihilation up-conversion luminescence is simpler and more convenient to operate in practical application compared with the prior art.
5. The temperature ratio fluorescent probe based on triplet state-triplet state annihilation up-conversion luminescence provided by the invention can visually see the change of the color of a material along with the temperature through naked eyes, so that the visualization of temperature sensing is realized.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
FIG. 1 shows a scanning electron microscope image of thermally activated up-conversion crystallites prepared in example 3.
FIG. 2 shows a scanning electron microscope image of the non-heat activated up-conversion crystallites prepared in example 3.
Fig. 3 shows a graph of the luminescence intensity of the heat-activated up-conversion microcrystal prepared in example 3 as a function of temperature, wherein (a) in fig. 3 is a spectrum of luminescence intensity as a function of temperature, and (b) is a graph of the maximum luminescence peak intensity as a function of temperature.
Fig. 4 shows a graph of luminescence intensity of the non-heat-activated up-conversion microcrystal prepared in example 3 as a function of temperature, wherein (a) in fig. 4 is a spectrum of luminescence intensity as a function of temperature, and (b) is a graph of maximum luminescence peak intensity as a function of temperature.
Fig. 5 shows a graph of the luminescence intensity of the mixed up-conversion crystallites prepared in example 3 as a function of temperature.
Fig. 6 shows a ratio fluorescence plot of the mixed up-conversion crystallites prepared in example 3.
Fig. 7 shows the luminescence colors at 223K and 300K, respectively, of the mixed up-conversion crystallites prepared in example 3.
Fig. 8 shows up-conversion luminescence spectra obtained by comparing the experimental group and the control group in experiment 1, wherein (a) in fig. 8 is an up-conversion luminescence spectrum of the experimental group, and (b) is an up-conversion luminescence spectrum of the control group.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments and the accompanying drawings. Like parts in the drawings are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Example 1
The embodiment provides a preparation method of a rare earth complex Yb (DBM) 3(H2 O, and the structure is shown as follows.
0.672G (3.0 eq) of dibenzoylmethane was dissolved in 70mL of acetone, 9mL of aqueous potassium hydroxide (0.5M) was added, heated to 60 ℃, refluxed for 30min, 0.539g of neodymium chloride (1.0 eq) dissolved in 15mL of water was added thereto, the reaction was continued for 2h, a yellow solid precipitated after the end of the reaction, filtered to obtain a solid, recrystallized with acetone and cyclohexane to obtain Yb (DBM) 3(H2 O), and the obtained crystals were identified by elemental analysis and FT-IR.
Elemental analysis calculated for C 45H35YbO7 (%) C62.79, H4.10; actual measurement value: c62.81, h 4.06.
IR(ATR)＝3401(st, O-H), 1605(st, C＝O), 809(st, Yb-O) cm-1。
Example 2
The embodiment provides a polynuclear rare earth complex Yb 5(DBM)10(OH)5, the structure of which is shown as follows.
0.448G (2.0 eq) of dibenzoyl ketone was dissolved in 38mL of ethanol, 3mL of aqueous sodium hydroxide (1M) was added, heated to 75 ℃, refluxed for 60min, 0.438g of neodymium nitrate (1.0 eq) dissolved in 9mL of water was added thereto, the reaction was continued for 8h, a yellow solid precipitated after the end of the reaction, filtered to obtain a solid, and recrystallized with ethanol and tetrahydrofuran to obtain Yb 5(DBM)10(OH)5, and the obtained crystals were identified by elemental analysis and FT-IR.
Elemental analysis calculated for C 150H115Yb5O25 (%) C56.11, h 3.64; actual measurement value: c56.23, h 3.71.
IR(ATR)＝3443(st, O-H), 1557(st, C＝O), 789(st, Yb-O) cm-1。
Example 3
The embodiment provides a temperature ratio fluorescent probe based on triplet-triplet annihilation up-conversion luminescence, and the preparation method comprises the following steps:
Preparation of heat-activated up-conversion crystallites: yb (DBM) 3(H2 O as a first photosensitizer and 9,10- (diphenylethynyl) anthracene (BPEA) as a first triplet annihilation agent are dispersed in 1mL of tetrahydrofuran solution under an air atmosphere, wherein the concentration of Yb (DBM) 3(H2 O) is 0.0011mmol/L, the concentration of 9,10- (diphenylethynyl) anthracene is 0.03mmol/L, the mixture is injected into water, solids are re-precipitated, the mixture is stirred for 5min at 1000r/min, the mixture is left for 2h, the mixture is centrifuged for 5min at 8000r/min, the precipitate is collected, and vacuum drying at 40 ℃ is carried out to obtain heat-activated up-conversion microcrystalline powder, the microcrystalline structure of which is represented by a scanning electron microscope, and the result is shown in a 1-5 mu m rod-shaped structure.
Preparation of non-heat activated up-conversion crystallites: in an air atmosphere, yb (DBM) 3(H2 O as a second photosensitizer and N, N' -di (ethylpropyl) perylene-3, 4,9, 10-tetracarboxylic acid (PDI) as a second triplet annihilation agent are dispersed in 1mL of tetrahydrofuran solution, wherein the concentration of Yb (DBM) 3(H2 O) is 0.004mmol/L, the concentration of PDI is 0.04mmol/L, the Yb (DBM) 3(H2 O) is injected into water, solids are re-precipitated, stirring is carried out for 5min at 1000r/min, standing is carried out for 2h, centrifugation is carried out for 5min at 8000r/min, precipitate is collected, vacuum drying is carried out at 20-40 ℃ to obtain non-thermal activation up-conversion microcrystalline powder, the microcrystalline structure of which is characterized by a scanning electron microscope, and the result is shown in a 5-10 mu m blade-shaped structure in a graph shown in figure 2.
And (3) screening out large particles of the two up-conversion microcrystalline powders by using a 100-mesh screen, mixing the screened two up-conversion microcrystalline powders according to the mass ratio of 1:1, and vibrating in an oscillator for 5min to obtain uniform mixed up-conversion microcrystalline powder, namely the temperature ratio fluorescent probe.
Up-conversion temperature-changing luminescence performance test of up-conversion microcrystalline powder
Under the anaerobic environment, the heat-activated up-conversion microcrystalline powder is placed at different temperatures to test the change of the up-conversion luminous intensity, and the non-heat-activated up-conversion microcrystalline powder is also tested under the anaerobic environment to test the change of the up-conversion luminous intensity at different temperatures, wherein the adopted excitation light wavelength is 980nm, and the result is shown in fig. 3 and 4.
As can be seen from fig. 3 and 4, the maximum luminescence peak position of the heat-activated up-conversion microcrystalline powder is 570nm, the luminescence peak intensity gradually increases with the increase of temperature, and the heat-activated up-conversion microcrystalline powder belongs to a heat-activated up-conversion system, the maximum luminescence peak position of the non-heat-activated up-conversion microcrystalline powder is 650nm, the luminescence peak intensity gradually decreases with the increase of temperature, and the heat-activated up-conversion microcrystalline powder belongs to a non-heat-activated up-conversion system, and the mixing experiment of the two up-conversion microcrystalline powder meets the basic condition as the ratio fluorescence.
Mixed up-conversion microcrystalline powder up-conversion temperature-change luminescence performance test
In an anaerobic environment, the mixed up-conversion microcrystalline powder, namely the temperature ratio fluorescent probe, is placed at different temperatures, the change condition of the luminous intensity along with the temperature is tested, the adopted excitation light wavelength is 980nm, and the result is shown in figure 5.
As can be seen from fig. 5, the maximum luminescence peak wavelengths of the mixed up-conversion microcrystalline powder are 570nm and 650nm, the luminescence intensities are respectively represented as I 570 and I 650,I570/I650, the ratio of the luminescence intensities is represented as I 570 and I 650,I570/I650, the change relation of I 570/I650 with temperature is shown in fig. 6, I 570/I650 increases linearly with the increase of temperature, the fitting formula is I 570/I650=0.01046T-1.9544,R2 = 0.99351, wherein T is temperature and K, the curve shows that the ratio fluorescence based on the two-component TTA up-conversion mixed microcrystalline powder has a temperature dependence, can be used as ratio fluorescence temperature sensing, and the relative sensitivity is 2.8%/K at 223K.
Mixed up-conversion microcrystalline powder up-conversion temperature-change luminescence color change test
In an anaerobic environment, the mixed up-conversion microcrystalline powder, namely, the temperature ratio fluorescent probe is sequentially placed under 223K and 300K, the adopted excitation light wavelength is 980nm, the luminescence color is shown in fig. 7, the luminescence color is yellow at 223K, the luminescence color is changed from yellow to orange at 300K, and the mixed up-conversion microcrystalline powder has the function of indicating the temperature through color change, namely, the temperature change is visualized.
Example 4
The present example provides a temperature ratio fluorescent probe based on triplet-triplet annihilation up-conversion luminescence, which was prepared in the same manner as in example 3, except that the mass ratio of the heat-activated up-conversion microcrystalline powder to the non-heat-activated up-conversion powder was changed to 1:10.
Up-conversion temperature-changing luminescence performance test of up-conversion microcrystalline powder
The test method is the same as that of example 3, the maximum luminescence peak position of the heat-activated up-conversion microcrystal powder is 570nm, the luminescence intensity of the heat-activated up-conversion microcrystal powder is gradually enhanced along with the increase of temperature, the maximum luminescence peak position of the non-heat-activated up-conversion microcrystal powder is 650nm, the luminescence intensity of the non-heat-activated up-conversion microcrystal powder is gradually reduced along with the increase of temperature, the non-heat-activated up-conversion microcrystal powder is a non-heat-activated up-conversion microcrystal powder, and the mixing experiment of the two up-conversion microcrystal powder meets the basic condition as ratio fluorescence.
Mixed up-conversion microcrystalline powder up-conversion temperature-change luminescence performance test
Test method the test method is the same as that of example 3, the maximum luminescence peak wavelength of the mixed up-conversion microcrystal powder is 570nm and 650nm respectively, the luminescence intensity is expressed as the ratio of I 570 and I 650,I570/I650, I 570/I650 is linear increase along with the temperature increase, fitting formula is I 570/650=0.01968T-3.6885,R2 = 0.99452, wherein T is temperature and unit is K, the curve shows that the ratio fluorescence based on the two-component TTA up-conversion mixed microcrystal has temperature dependence, can be used as ratio fluorescence temperature sensing, and the relative sensitivity at 223K is tested to be 2.8%/K.
Mixed up-conversion microcrystalline powder up-conversion temperature-change luminescence color change test
The test method was the same as in example 3, and it was found that the emission color was yellow at 223K and changed from yellow to orange at 300K, indicating that the mixed up-conversion microcrystalline powder had a function of indicating temperature by a color change, i.e., a temperature change was visualized.
Example 5
This example provides a temperature ratio fluorescent probe based on triplet-triplet annihilation up-conversion luminescence, which is prepared in the same manner as in example 3, except that the first triplet annihilation agent is replaced with 9, 10-bis [ (triisopropylsilyl) ethynyl ] anthracene, and the molar ratio of the first photosensitizer to the first triplet annihilation agent is changed to 1:1.
Up-conversion microcrystalline powder up-conversion temperature-change luminescence performance test
The test method is the same as that of example 3, the maximum luminescence peak position of the heat-activated up-conversion microcrystal powder is 520nm, the luminescence intensity of the heat-activated up-conversion microcrystal powder is gradually enhanced along with the increase of temperature, the maximum luminescence peak position of the non-heat-activated up-conversion microcrystal powder is 650nm, the luminescence intensity of the non-heat-activated up-conversion microcrystal powder is gradually reduced along with the increase of temperature, the non-heat-activated up-conversion microcrystal powder is the non-heat-activated up-conversion microcrystal powder, and the mixing experiment of the two up-conversion microcrystal powder meets the basic condition as the ratio fluorescence.
Mixed up-conversion microcrystalline powder up-conversion temperature-change luminescence performance test
Test method the test method is the same as that of example 3, the maximum luminescence peak wavelength of the mixed up-conversion microcrystal powder is respectively at 520nm and 650nm, the luminescence intensity is respectively expressed as I 520 and I 650,I520/I650 and is expressed as the ratio of the two intensities, I 520/I650 is linearly increased along with the temperature increase, the fitting formula is I 520/650=0.02400T-4.0926,R2 = 0.99431, wherein T is temperature and is K, the curve shows that the ratio fluorescence based on the two-component TTA up-conversion mixed microcrystal has the dependence on temperature, can be used as the ratio fluorescence temperature sensing, and the relative sensitivity at 223K is tested to be 1.9%/K.
Mixed up-conversion microcrystalline powder up-conversion temperature-change luminescence color change test
Test method as in example 3, it was found that the emission color was green at 223K and changed from green to orange at 300K, indicating that the mixed up-conversion microcrystalline powder had a function of indicating temperature by color change, i.e., temperature change was visualized.
Example 6
This example provides a temperature ratio fluorescent probe based on triplet-triplet annihilation up-conversion luminescence, which is prepared in the same manner as in example 3, except that the second triplet annihilation agent is changed to N, N' -di-N-octyl-3, 4,9, 10-perylene tetracarboxylic diimide (ODI), and the molar ratio of the first photosensitizer to the first triplet annihilation agent is changed to 1:40.
Up-conversion temperature-changing luminescence performance test of up-conversion microcrystalline powder
The test method is the same as that of example 3, the maximum luminescence peak position of the heat-activated up-conversion microcrystal powder is 570nm, the luminescence intensity of the heat-activated up-conversion microcrystal powder is gradually enhanced along with the increase of temperature, the maximum luminescence peak position of the non-heat-activated up-conversion microcrystal powder is 600nm, the luminescence intensity of the non-heat-activated up-conversion microcrystal powder is gradually reduced along with the increase of temperature, the non-heat-activated up-conversion microcrystal powder is subjected to a mixing experiment, and the two up-conversion microcrystal powder meets the basic condition of being taken as ratio fluorescence.
Mixed up-conversion microcrystalline powder up-conversion temperature-change luminescence performance test
Test method the test method is the same as that of example 3, the maximum luminescence peak wavelength of the mixed up-conversion microcrystal powder is 570nm and 600nm respectively, the luminescence intensity is expressed as the ratio of I 570 and I 600,I570/I600, I 570/I600 is linear increase along with the temperature increase, fitting formula is I 570/600=0.40968T-75.549,R2 = 0.98322, wherein T is temperature and unit is K, the curve shows that the ratio fluorescence based on the two-component TTA up-conversion mixed microcrystal has temperature dependence, can be used as ratio fluorescence temperature sensing, and the relative sensitivity at 223K is tested to be 2.6%/K.
Mixed up-conversion microcrystalline powder up-conversion temperature-change luminescence color change test
The test method was the same as in example 3, and it was found that the emission color was yellow at 223K and changed from yellow to orange at 300K, indicating that the mixed up-conversion microcrystalline powder had a function of indicating temperature by a color change, i.e., a temperature change was visualized.
Example 7
This example provides a temperature ratio fluorescent probe based on triplet-triplet annihilation up-conversion luminescence, and the preparation method thereof is the same as in example 5, except that the second triplet annihilation agent is changed to N, N' -di-N-octyl-3, 4,9, 10-perylene tetracarboxylic diimide (ODI).
Up-conversion microcrystalline powder up-conversion temperature-change luminescence performance test
The test method is the same as that of example 3, the maximum luminescence peak position of the heat-activated up-conversion microcrystal powder is 520nm, the luminescence intensity of the heat-activated up-conversion microcrystal powder is gradually enhanced along with the increase of temperature, the maximum luminescence peak position of the non-heat-activated up-conversion microcrystal powder is 600nm, the luminescence intensity of the non-heat-activated up-conversion microcrystal powder is gradually reduced along with the increase of temperature, the non-heat-activated up-conversion microcrystal powder is the non-heat-activated up-conversion microcrystal powder, and the mixing experiment of the two up-conversion microcrystal powder meets the basic condition as the ratio fluorescence.
Mixed up-conversion microcrystalline powder up-conversion temperature-change luminescence performance test
Test method the test method is the same as that of example 3, the maximum luminescence peak wavelength of the mixed up-conversion microcrystal powder is respectively at 520nm and 600nm, the luminescence intensity is respectively expressed as I 520 and I 600,I520/I600 and is expressed as the ratio of the two intensities, I 520/I600 is linearly increased along with the temperature increase, the fitting formula is I 520/600=0.1012T-19.7344,R2 = 0.99621, wherein T is temperature and is K, the curve shows that the ratio fluorescence based on the two-component TTA up-conversion mixed microcrystal has the dependence on temperature, can be used as the ratio fluorescence temperature sensing, and the relative sensitivity at 223K is tested to be 3.6%/K.
Mixed up-conversion microcrystalline powder up-conversion temperature-change luminescence color change test
Test method as in example 3, it was found that the emission color was green at 223K and changed from green to orange at 300K, indicating that the mixed up-conversion microcrystalline powder had a function of indicating temperature by color change, i.e., temperature change was visualized.
Example 8
This example provides a temperature ratio fluorescent probe based on triplet-triplet annihilation, which is produced by the same method as in example 5, except that the second triplet annihilation agent is changed to rubrene, the molar ratio of the first photosensitizer to the first triplet annihilation agent is changed to 1:5, and the molar ratio of the second photosensitizer to the second triplet annihilation agent is changed to 1:35.
Up-conversion microcrystalline powder up-conversion temperature-change luminescence performance test
The test method is the same as that of example 3, the maximum luminescence peak position of the heat-activated up-conversion microcrystal powder is 520nm, the luminescence intensity of the heat-activated up-conversion microcrystal powder is gradually enhanced along with the increase of temperature, the maximum luminescence peak position of the non-heat-activated up-conversion microcrystal powder is 580nm, the luminescence intensity of the non-heat-activated up-conversion microcrystal powder is gradually reduced along with the increase of temperature, the non-heat-activated up-conversion microcrystal powder is a non-heat-activated up-conversion microcrystal powder, and the mixing experiment of the two up-conversion microcrystal powder meets the basic condition as ratio fluorescence.
Mixed up-conversion microcrystalline powder up-conversion temperature-change luminescence performance test
Test method the test method is the same as that of example 3, the maximum luminescence peak wavelength of the mixed up-conversion microcrystal powder is respectively at 520nm and 580nm, the luminescence intensity is respectively expressed as I 520 and I 580,I520/I580 and is expressed as the ratio of the two intensities, I 520/I580 is linearly increased along with the increase of temperature, the fitting formula is I 520/580=1.1227T-225.588,R2 = 0.99368, wherein T is temperature and is K, the curve shows that the ratio fluorescence based on the two-component TTA up-conversion mixed microcrystal has the dependence on temperature, can be used as the ratio fluorescence temperature sensing, and the relative sensitivity at 223K is tested to be 4.5%/K.
Mixed up-conversion microcrystalline powder up-conversion temperature-change luminescence color change test
Test method as in example 3, it was found that the emission color was green at 223K and changed from green to yellow at 300K, indicating that the mixed up-conversion microcrystalline powder had a function of indicating temperature by color change, i.e., temperature change was visualized.
Example 9
The present embodiment provides a temperature ratio fluorescent probe based on triplet-triplet annihilation up-conversion luminescence, and the preparation method thereof is the same as that of embodiment 3, except that the first photosensitizer is changed to Yb 5(DBM)10(OH)5, the molar ratio of the first photosensitizer to the first triplet annihilation agent is changed to 1:1, and the molar ratio of the second photosensitizer to the second triplet annihilation agent is changed to 1:4.
Up-conversion temperature-changing luminescence performance test of up-conversion microcrystalline powder
The test method is the same as that of example 3, the maximum luminescence peak position of the heat-activated up-conversion microcrystal powder is 570nm, the luminescence intensity of the heat-activated up-conversion microcrystal powder is gradually enhanced along with the increase of temperature, the maximum luminescence peak position of the non-heat-activated up-conversion microcrystal powder is 650nm, the luminescence intensity of the non-heat-activated up-conversion microcrystal powder is gradually reduced along with the increase of temperature, the non-heat-activated up-conversion microcrystal powder is a non-heat-activated up-conversion microcrystal powder, and the mixing experiment of the two up-conversion microcrystal powder meets the basic condition as ratio fluorescence.
Mixed up-conversion microcrystalline powder up-conversion temperature-change luminescence performance test
Test method the test method is the same as that of example 3, the maximum luminescence peak wavelength of the mixed up-conversion microcrystal powder is 570nm and 650nm respectively, the luminescence intensity is expressed as the ratio of I 570 and I 650,I570/I650, I 570/I650 is linear increase along with the temperature increase, fitting formula is I 570/650=0.01134T-2.1712,R2 = 0.99921, wherein T is temperature and unit is K, the curve shows that the ratio fluorescence based on the two-component TTA up-conversion mixed microcrystal has dependence on temperature, can be used as ratio fluorescence temperature sensing, and the relative sensitivity at 223K is 3.2%/K.
Mixed up-conversion microcrystalline powder up-conversion temperature-change luminescence color change test
The test method was the same as in example 3, and it was found that the emission color was yellow at 223K and changed from yellow to orange at 300K, indicating that the mixed up-conversion microcrystalline powder had a function of indicating temperature by a color change, i.e., a temperature change was visualized.
Example 10
This example provides a temperature ratio fluorescent probe emitting light by triplet-triplet annihilation up-conversion, which is prepared in the same manner as in example 3, except that the first photosensitizer is changed to palladium (II) tetraphenyltetraporphyrin, the first triplet annihilation agent is changed to 9, 10-diphenylanthracene, the second photosensitizer is changed to palladium (II) tetraphenyltetraphenyltetraporphyrin, the second triplet annihilation agent is changed to rubrene, the molar ratio of the first photosensitizer to the first triplet annihilation agent is changed to 1:100, the molar ratio of the second photosensitizer to the second triplet annihilation agent is changed to 1:200, and the wavelength of excitation light used is changed to 635nm.
Up-conversion temperature-changing luminescence performance test of up-conversion microcrystalline powder
The test method is the same as that of example 3, except that the excitation light wavelength is 635nm, the maximum luminescence peak position of the heat-activated up-conversion microcrystal powder is 470nm, the luminescence intensity of the heat-activated up-conversion microcrystal powder is gradually increased along with the temperature increase, the heat-activated up-conversion microcrystal powder belongs to a heat-activated up-conversion system, the maximum luminescence peak position of the non-heat-activated up-conversion microcrystal powder is 580nm, the luminescence intensity of the non-heat-activated up-conversion microcrystal powder is gradually reduced along with the temperature increase, and the mixing experiment of the two up-conversion microcrystal powder meets the basic condition as ratio fluorescence.
Mixed up-conversion microcrystalline powder up-conversion temperature-change luminescence performance test
The test method is identical to example 3, except that the excitation light wavelength is 635nm, the maximum luminescence peak wavelength of the mixed up-conversion microcrystal powder is 470nm and 580nm respectively, the luminescence intensities are respectively represented as the ratio of I 470 to I 580,I470/I580, I 470/I580 increases linearly with the increase of temperature, the fitting formula is I 470/580=0.02482T-4.4169,R2 = 0.99945, T is temperature and K, the curve shows that the ratio fluorescence based on the two-component TTA up-conversion mixed microcrystal has the dependence on temperature, can be used as the ratio fluorescence temperature sensing, and the relative sensitivity at 223K is 2.2%/K.
Mixed up-conversion microcrystalline powder up-conversion temperature-change luminescence color change test
The test method was identical to example 3 except that the excitation light wavelength used was 635nm, and the emission color was found to be blue at 223K, and changed from blue to yellow at 300K, indicating that the mixed up-conversion microcrystalline powder had a function of indicating temperature by color change, i.e., temperature change was visualized.
Example 11
This example provides a test application of a temperature ratio fluorescent probe in an aqueous system environment, the temperature ratio fluorescent probe was prepared in the same manner as in example 3, and then 5mg of mixed up-conversion crystallites were dispersed in 5mL of an aqueous solution containing Sodium Dodecyl Sulfate (SDS) at a concentration of 10g/L for subsequent testing.
Up-conversion temperature-changing luminescence performance test of up-conversion microcrystalline powder
The test method is identical to example 3, except that the test temperature range is 273K-300K, the maximum luminescence peak position of the tested heat-activated up-conversion microcrystalline powder is 570nm, the luminescence intensity of the test heat-activated up-conversion microcrystalline powder is gradually increased along with the temperature increase, the test method belongs to a heat-activated up-conversion system, the maximum luminescence peak position of the non-heat-activated up-conversion microcrystalline powder is 650nm, the luminescence intensity of the test heat-activated up-conversion microcrystalline powder is gradually reduced along with the temperature increase, the test method belongs to a non-heat-activated up-conversion system, and the mixing experiment of the two up-conversion microcrystalline powder accords with the basic condition as ratio fluorescence.
Mixed up-conversion microcrystalline powder up-conversion temperature-change luminescence performance test
The test method is identical to example 3, except that the test temperature range is 273K-300K, the maximum luminescence peak wavelength of the up-conversion microcrystalline powder aqueous phase solution after test is 570nm and 650nm respectively, the luminescence intensity is represented as the ratio of I 570 and I 650,I570/I650 respectively, I 570/I650 increases linearly with the increase of temperature, the fitting formula is I 570/650=0.01055T-1.6784,R2 = 0.98521, T is temperature, K, the curve shows that the ratio fluorescence based on the two-component TTA up-conversion mixed microcrystalline aqueous phase solution has a temperature dependence, can be used as ratio fluorescence temperature sensing, and the relative sensitivity at 273K is 1.5%/K after test.
Mixed up-conversion microcrystalline powder up-conversion temperature-change luminescence color change test
The test method is identical to that of example 3, except that the test temperature is in the range of 273K-300K, the luminescent color is found to be yellow at 273K, and the luminescent color is changed from yellow to orange at 300K, which indicates that the mixed up-conversion microcrystalline aqueous phase solution has the function of indicating the temperature through color change, namely, the temperature change is visualized.
Comparative experiment 1
In order to further study the influence of the mixed up-conversion microcrystalline powder preparation method on the contrast ratio fluorescence, an experiment group and a control group are provided in the comparison experiment, and the luminous performance of the comparison experiment is analyzed and compared:
the experimental group was prepared exactly in the same manner as the temperature ratio fluorescent probe of example 3.
The control group was prepared as follows:
1) Preparing a heat-activated up-conversion system: taking Yb (DBM) 3(H2 O as a first photosensitizer, taking BPEA as a first triplet annihilation agent, and adopting toluene as a solvent to disperse the first photosensitizer and the first triplet annihilation agent, wherein the concentration of the first photosensitizer is 0.0011mmol/L, and the concentration of the first triplet annihilation agent is 0.03mmol/L, so that a solution-state heat-activated up-conversion system is configured;
2) Preparing a non-heat-activated up-conversion system: taking Yb (DBM) 3(H2 O as a second photosensitizer, taking PDI as a second triplet annihilation agent, and adopting toluene as a solvent to disperse the second photosensitizer and the second triplet annihilation agent, wherein the concentration of the second photosensitizer is 0.004mmol/L, and the concentration of the second triplet annihilation agent is 0.04mmol/L, so that a solution state non-heat-activated up-conversion system is configured;
3) The two up-conversion systems are mixed and deoxygenated, namely argon bubbling deoxygenation is carried out for 1h.
As shown in FIG. 8, the up-conversion luminescence of the control group is converted into a single luminescence peak under the pumping of 980nm excitation light source, and the experimental group is two luminescence peaks, which indicates that the preparation method provided by the invention avoids the disorder of energy transfer (such as the condition that the energy of the first photosensitizer is transferred to the second triplet annihilator) caused by excessive system components, and simultaneously the two luminescence peaks can be used for ratio fluorescence temperature sensing.
Comparative experiment 2
In order to study the ratio fluorescence influence of up-conversion materials with two different luminescent colors on visual temperature response, the comparison experiment provides an experiment group, a control group 1 and a control group 2, and the luminescent properties of the experiment group, the control group 1 and the control group 2 are analyzed and compared:
the experimental group was prepared exactly in the same manner as the temperature ratio fluorescent probe of example 3.
Control group 1: only the heat-activated up-conversion crystallites of example 3 were used, and a single up-conversion system was used as a ratio fluorescent probe to test the change in luminescence color with temperature.
Control group 2: only the non-heat activated up-conversion crystallites of example 3 were used, and a single up-conversion system was used as a ratio fluorescent probe to test the change in luminescence color with temperature.
The results of the study are shown in Table 1, and also in 980nm excitation light source pumping, the control group 1 and the control group 2 did not change in color when the ambient temperature was changed from 223K to 300K, but only in the experimental group when both up-conversion crystallites were present at the same time.
TABLE 1
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (10)
1. A temperature ratio fluorescent probe based on triplet-triplet annihilation up-conversion luminescence, characterized in that the temperature ratio fluorescent probe comprises thermally-activated up-conversion crystallites and non-thermally-activated up-conversion crystallites; the thermally-activated up-conversion crystallites comprise a first photosensitizer and a first triplet annihilator, and the non-thermally-activated up-conversion crystallites comprise a second photosensitizer and a second triplet annihilator;
Wherein the excitation wavelength of the first photosensitizer is the same as that of the second photosensitizer, and the first photosensitizer and the second photosensitizer are selected from metal complexes absorbed in a near infrared region of 600-1000 nm.
2. The temperature ratio fluorescent probe of claim 1, wherein the first photosensitizer and the second photosensitizer are selected from any one of tetraphenyl tetrabenzoporphyrin metal complex of palladium or platinum, rare earth complex of ytterbium as photosensitive core, rare earth complex of neodymium as photosensitive core, rare earth complex of thulium as photosensitive core;
The first triplet annihilation agent is selected from one or more of 9, 10-diphenyl anthracene or a derivative thereof, 9,10- (diphenylethynyl) anthracene or a derivative thereof, and 9, 10-bis [ (triisopropylsilyl) ethynyl ] anthracene;
The second triplet annihilator is selected from one or more of rubrene, perylene tetracarboxylic diimide or derivatives thereof.
3. The temperature ratio fluorescent probe of claim 1, wherein the first photosensitizer and the second photosensitizer are selected from a diketone complex with ytterbium as a photoactive core or palladium (II) tetraphenyl tetrabenzoporphyrin.
4. The temperature ratio fluorescent probe of claim 1, wherein the molar ratio of the first photosensitizer to the first triplet annihilator is 1:1 to 1:500; the molar ratio of the second photosensitizer to the second triplet annihilation agent is 1:1-1:300.
5. The temperature ratio fluorescent probe of claim 1, wherein the mass ratio of thermally activated up-conversion crystallites and non-thermally activated up-conversion crystallites is between 1:1 and 1:1000.
6. The temperature ratio fluorescent probe of claim 1, wherein the mass ratio of thermally activated up-conversion crystallites and non-thermally activated up-conversion crystallites is from 1:1 to 1:50.
7. The method for preparing a temperature ratio fluorescent probe according to any one of claims 1 to 6, comprising the steps of:
dispersing a first photosensitizer and a first triplet annihilation agent in an organic solvent, then adding the organic solvent into water, stirring until the mixture is uniform, standing, centrifuging, and drying to obtain heat-activated up-conversion microcrystals;
Dispersing a second photosensitizer and a second triplet annihilation agent in an organic solvent, then adding the organic solvent into water, stirring until the mixture is uniform, standing, centrifuging, and drying to obtain non-heat-activated up-conversion microcrystals;
and fully mixing the heat-activated up-conversion microcrystals and the non-heat-activated up-conversion microcrystals in proportion to obtain the temperature ratio fluorescent probe.
8. The method according to claim 7, wherein the organic solvent is one or more selected from tetrahydrofuran, chloroform, dimethyl sulfoxide, and N, N-dimethylformamide.
9. Use of a temperature ratio fluorescent probe according to any one of claims 1-6 in the field of temperature sensing.
10. The use according to claim 9, wherein the temperature ratio fluorescent probe is used in visual non-contact temperature monitoring of the interior of a material or device.
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| US20130034122A1 (en) * | 2010-04-07 | 2013-02-07 | Research Triangle Institute, International | Fluorescence based thermometry |
| CN107573928A (en) * | 2017-10-09 | 2018-01-12 | 中国科学院理化技术研究所 | Solid-state up-conversion luminescent material based on triplet-triplet annihilation and preparation method thereof |
| US20180106785A1 (en) * | 2015-03-24 | 2018-04-19 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Capsule suitable for non-invasive simultaneous oxygen content and temperature sensing in a living object |
| CN109180692A (en) * | 2018-08-26 | 2019-01-11 | 苏州科技大学 | Converting system and preparation method thereof and the application in preparation temperature sensor on Thermo-sensitive |
| CN114656966A (en) * | 2022-04-15 | 2022-06-24 | 中国科学院福建物质结构研究所 | Four-layer core-shell structure nano material and preparation method and application thereof |
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| US20130034122A1 (en) * | 2010-04-07 | 2013-02-07 | Research Triangle Institute, International | Fluorescence based thermometry |
| US20180106785A1 (en) * | 2015-03-24 | 2018-04-19 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Capsule suitable for non-invasive simultaneous oxygen content and temperature sensing in a living object |
| CN107573928A (en) * | 2017-10-09 | 2018-01-12 | 中国科学院理化技术研究所 | Solid-state up-conversion luminescent material based on triplet-triplet annihilation and preparation method thereof |
| CN109180692A (en) * | 2018-08-26 | 2019-01-11 | 苏州科技大学 | Converting system and preparation method thereof and the application in preparation temperature sensor on Thermo-sensitive |
| CN114656966A (en) * | 2022-04-15 | 2022-06-24 | 中国科学院福建物质结构研究所 | Four-layer core-shell structure nano material and preparation method and application thereof |
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